EP3559133B1 - A coating composition system, the preparation method, and the use thereof - Google Patents

A coating composition system, the preparation method, and the use thereof Download PDF

Info

Publication number
EP3559133B1
EP3559133B1 EP16925032.1A EP16925032A EP3559133B1 EP 3559133 B1 EP3559133 B1 EP 3559133B1 EP 16925032 A EP16925032 A EP 16925032A EP 3559133 B1 EP3559133 B1 EP 3559133B1
Authority
EP
European Patent Office
Prior art keywords
pass pass
resins
alkenyl
group
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16925032.1A
Other languages
German (de)
French (fr)
Other versions
EP3559133A4 (en
EP3559133A1 (en
Inventor
Xiaoguang HAN
Junbiao Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel Coatings International BV
Original Assignee
Akzo Nobel Coatings International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Coatings International BV filed Critical Akzo Nobel Coatings International BV
Publication of EP3559133A1 publication Critical patent/EP3559133A1/en
Publication of EP3559133A4 publication Critical patent/EP3559133A4/en
Application granted granted Critical
Publication of EP3559133B1 publication Critical patent/EP3559133B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002—Pretreatement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • This invention relates to a coating composition system for forming a complex coating structure including a primer coating layer and a top coating layer onto a substrate, specifically to a liquid silicone rubber coating composition system for forming a stain resistant and soft tactile texture complex coating structure, and its preparation method and application in consumer electrics, automobile industry and other industries.
  • Plastics and metal materials are widely used in consumer electrics, automobile industry and other industries such as architecture. They are made into housings, cases, shells, covers, hulls of a lot of subjects like computers, phones, home appliances, automobile parts, and walls of buildings.
  • Typical plastic materials include polycarbonate (PC), acrylonitrile butadiene styrene (ABS) copolymer, polymethyl methacrylate (PMMA), polyamide (PA), glass fibre and/or carbon fibre reinforced plastics, and soft plastic materials such as thermal plastic polyurethane (TPU), etc.
  • Typical metals substrates include aluminium, steel, anodized aluminium oxide (AAO), aluminium-magnesium alloy, etc.
  • the materials as a substrate usually need to be covered with a coating for better property or additional protection. For example, coatings with tactile texture are required by customers in many industries.
  • Soft resins have been used as the main material in coating compositions to provide the resulting coatings with soft tactile texture.
  • Typical soft resins include polyester polyols, polyurethane polyols, polyurethane dispersions, acrylic latex etc.
  • the soft resin system may be solvent based or water based.
  • WO201289827 discloses a polyurethane soft touch coating composition characterized in that it comprises the reaction product of (A) a non-hydrolysable polyol binder, and (B) an organic polyisocyanate.
  • Elastic powders have been also used in coating compositions to provide the resulting coatings with soft feel and matting effects.
  • Typical elastic powders include silicone rubber powders or microspheres, microspheres of expansible materials, etc. for example, US20060021888 discloses a coating composition wherein silicone rubber particles are added to a traditional resin coating system to obtain a coating with soft tactile texture and antiglare effects.
  • the coatings are provided with soft tactile texture and thus have been widely used in the coating industry. Due to their poor stain resistance property, however, the practical application has been limited. Especially for applications on dark color substrates, it is normally impractical to use coatings with soft resins or elastic powders, as stain marks are more obvious in a dark color background.
  • US20070137524 discloses a new resin system of polybutadiene polyol and polyolefinic acid. It is used in soft feel coating compositions, to increase discoloration resistance, heat resistance, yellowing resistance and anti-fouling properties of the resulting coatings. Although the composition achieves better performance upon modifications, the stain resistance of the resulting coatings is still not satisfactory.
  • silicone rubber coatings are frequently used in varies of industries, due to their good electric insulation, physical strength and elasticity, soft feel, stain resistance etc.
  • the silicone rubber systems are mainly based on two reaction mechanisms: condensation reaction and addition reaction.
  • the former is a reaction between hydroxyl silicone oils with different silanes, and the latter is a reaction between vinyl silicone oils with active hydrogen silicone oils. Both of the two silicone rubber systems are widely used in coating industry.
  • CN1036279 discloses a sparkling silicone elastic coating for optical fiber protection and label materials for ceramic and metals.
  • the composition comprises methyl vinyl polysiloxane, vinyl MQ reinforcing agent, organohydrogenpolysiloxane, platinum catalyst, stabilizer, and pigments. Based on a thermal cure system, the coating composition requires a curing temperature as high as from 430 °C to 480 °C.
  • Silicone rubbers may also be used for fabrics, textiles and leathers because of their heat and weather resistance, water repellence, softness, cohesion, flexibility, etc.
  • EP2009059 discloses a liquid silicone rubber coating composition for curtain airbags.
  • the coating coating composition comprising (A) an organopolysiloxane containing silicon bonded alkenyl radicals, (B) an organohydrogenpolysiloxane containing Si-H radicals, (C) an addition reaction catalyst, (D) finely divided silica, (E) an organosilicon compound containing epoxy and alkoxy radicals, (F) an organic titanium, zirconium or aluminum compound, and (G) a silanol-_containing silane or siloxane compound is coated on a surface of an airbag base fabric and cured to form a rubber coating layer thereon.
  • JP2005296697A discloses a tactile coating on a substrate formed using a primer layer of a hydrosilylation cure silicone and a top layer of a polyurethane or silicone hydrosilylation curing polymer.
  • the present invention provides for an article coated with a coating composition system in accordance with claim 1 suitable for forming a stain resistant and soft tactile texture coating onto a variety of substrate materials including plastic materials, metal materials, ceramic materials, and concrete materials.
  • the coating composition system can be cured under mild curing conditions, and provide the resulting coating with excellent properties in terms of adhesion to the substrates, strength, and abrasion resistance.
  • the present invention also provides for a method tor forming a stain resistant and soft tactile coating system onto a substrate in accordance with claim 10, as well as the specific articles comprising the coating in accordance with claim 11.
  • the coating composition system comprises two separate coating compositions, wherein the first coating composition is to form a primer coating onto a substrate, and the second coating composition is to form a top coating onto the primer coating.
  • the primer coating serves as a middle layer between the substrate and top coating film, to improve the adhesion of the coating layers to the substrate.
  • the first composition is applied onto a substrate and cured to form a primer coating
  • the second coating composition is consequently applied onto the primer coating and cured to form a top coating.
  • the first coating composition according to the present invention includes: a hydroxyl resin, a hardener resin having functional groups which react with hydroxyl groups of the hydroxyl resin, an optional catalyst for the reaction between the resins, an optional adhesion promoter, optional additives, fillers, extenders, pigments and toners.
  • One or more resins with hydroxyl groups are used as the main ingredient of the first coating composition.
  • Typical resins that are suitable for use in the present invention include alkyd resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, and modified silicone resins. The resins can be used alone or in combination.
  • the first coating composition comprises one or more hardener resins having functional groups which react with the hydroxyl resins.
  • Typical resins that are suitable for use in the present invention include amino resins, isocyanates, and melamine resins.
  • the hardener resins are selected from poly-isocyanates, dimer-isocyanates, trimer-isocyanates, and biuret- isocyanates. The hardener resins can be used alone or in combination.
  • the molar ratio of hydroxyl groups of the hydroxyl resin is excessive over the molar ratio of the functional groups of the hardener resin in the first composition.
  • the excessive hydroxyl groups may further react with other functional groups in the second coating composition, such as Si-H groups, as shown below: ⁇ Si-H + HO-R ⁇ ⁇ Si-O-R + H 2
  • the reaction between the excessive hydroxyl groups of the first coating composition and the other functional groups in the second coating composition helps to improve the adhesion between coating layers and the substrate.
  • catalysts may be added into the first coating composition, to facilitate the reaction between the resins.
  • the catalysts are selected according to the resin system used in the first coating composition.
  • Typical catalysts that are suitable for use in the present invention include organic cobalt catalysts and manganese catalysts for alkyd resins, organic tin catalysts for polyurethane resins.
  • Adhesion promoters are added into the first coating composition to enhance the adhesion between the coating layers and the substrate.
  • Typical adhesion promoters that are suitable for use in the present invention include silanes with functional groups, such as epoxy silanes, amino silanes, and alkenyl silanes; organic metal compounds, such as titanates, zirconates, aluminates; resins with a hydroxyl value of from 100 mgKOH/g to 300 mgKOH/g, an acid value of from 20 mgKOH/g to 200mgKOH/g, or phosphate resins.
  • different additives can be further added into the first coating composition, such as levelling agent, defoaming agent etc.
  • fillers, extenders, pigments and toners can also be added into the first coating composition.
  • the addition of these materials helps to, for instance, reduce the cost, provide the coating film with desired colour effects. It should be noticed that these materials are not necessarily added into the first coating composition.
  • Typical fillers and extenders include CaCO 3 , talc powder, BaSO 4 , mica powder, kaolin powder, and glass powder.
  • Typical pigments and toners include both inorganic pigments and organic pigments which are commonly used in coating industry. In order to provide the resulting coating film with a metal like visual effect or pearl like visual effect, metal powder and pearl powders can also be added into the first coating composition.
  • solvents used in the first coating composition there is no special requirement or limitation to solvents used in the first coating composition.
  • solvents used in coating and paint industry such as alcohols, ethers, esters, ketones, alkanes, aromatic hydrocarbons, or a combination there of, are suitable for use in the present invention as well.
  • the second coating composition according to the present invention includes: an alkenyl containing polysiloxane of defined alkenyl content, a Si-H bond containing polysiloxane, a hydrosilylation catalyst, an optional reinforcing agent, an optional reaction inhibitor, optional matting agents, haptic agents, fillers, extenders, and pigments.
  • the curing mechanism of the second coating composition is based on an addition reaction curing process, wherein hydrosilylation takes place between the alkenyl groups of the alkenyl containing polysiloxane and the Si-H groups of the Si-H bond containing polysiloxane, at the presence of an organic precious metal catalyst.
  • R represents an alkyl group having 1 ⁇ 8 carbon atoms, or an alkenyl group having 2 ⁇ 10 carbon atoms, which may be selected from, for example, methyl, ethyl, butyl, phenyl, etc., and vinyl, allyl, buyenyl, pentenyl, hexenyl, heptenyl, etc., preferably R is methyl or vinyl;
  • R 1 and R 3 each independently represents an alkyl group having 1 ⁇ 8 carbon atoms, which may be selected from, for example, methyl, ethyl, butyl, phenyl, etc., preferably R 1 and R 3 are methyl;
  • R 2 represents an alkenyl group having 2 ⁇ 10 carbon atoms, which may be selected from, for example, vinyl, allyl, buyenyl, pentenyl, hexenyl, hep
  • the alkenyl containing polysiloxane is selected such that the viscosity of the alkenyl containing polysiloxane is not less than 1000 Cp at 25°C, preferably not less than 5,000 Cp at 25 °C, and meanwhile not greater than -500,000Cp at 25°C, preferably not greater than 100,000 cP at 25°C. Unless otherwise specified, said viscosity of the alkenyl containing polysiloxane is measured according to ASTM D2225. It has been observed that alkenyl containing polysiloxanes within the defined ranges helped to improve the strength of resulting coatings.
  • the alkenyl containing polysiloxane is selected such that the alkenyl content is not less than 0.2mmol/g, and meanwhile, not greater than 5.0mmol/g, preferably not greater than 3.0 mmol/g. It has been observed that alkenyl containing polysiloxanes within the defined ranges helped to improve the strength and tactile texture of the resulting coatings. Specifically, alkenyl containing polysiloxanes with an alkenyl content lower than 0.02mmol/g resulted in soft coating layers with poor strength, and alkenyl containing polysiloxanes with an alkenyl content higher than 5.0mmol/g resulted in hard coating layers with little soft feel and tactile texture.
  • Si-H bond containing polysiloxane suitable for use in the present invention is shown as the formula (II) below
  • a reinforcing agent is added into the second coating composition to further enhance the strength of resulting coatings.
  • the reinforcing agent selected from one or more of the group consisting of silica, mono-functional auad-functional silicone resins (MQ silicone resins), polyhedral oligomeric silsesquioxane (POSS), carbon black, and fibers.
  • any silica material containing SiO 2 can be used as the reinforcing agent of the second coating composition according to the present invention.
  • the silica material is selected from fumed silica, precipitated silica and quartz powders, which can be used alone or in combination. More preferably silica material is selected from fumed silicas which have gone through surface treatment with silanes.
  • the silica material is selected such that its BET surface area is between 500-400m 2 /g, preferably between 150-300m 2 /g, its primary particle size is between 5-50nm, and its average particle size is below 20um, preferably below 10um.
  • MQ silicone resins may also be added as the reinforcing agent into the second coating composition.
  • MQ silicone resins are meant to represent a broad range of hydrolytic condensation products of mono-functional silane (M) and Quad-functional silane (Q). Due to their three-dimensional network structure, MQ silicone resins may provide the resulting coatings with outstanding properties such as high hardness, antifriction, weathering ageing resistance, and may help reinforce the resulting coatings.
  • MQ resins There is no special requirement or limitation to MQ resins for use as the reinforcing agent in the second coating composition according to the present invention, yet MQ resins with alkenyl groups and active hydrogen groups are preferred.
  • reinforcing agents like POSS, carbon black, and fibers may also be used alone or in combination with the above mentioned silica materials and MQ silicone resins as the reinforcing agent in the second coating composition according to the present invention.
  • addition reaction catalyst is further added into the second composition.
  • the addition reaction catalyst is not particularly limited as long as it promotes hydrosilylation reaction between an alkenyl group and a Si-H group.
  • Typical catalysts that are suitable for use in the present invention are selected from, but not limited to, platinum compounds, palladium compounds, rhodium compounds, and ruthenium compounds, wherein platinum compounds are preferred.
  • an effective amount of the catalyst is between 0.1% to 2.5% in relation to the total weight of silicones( ⁇ 20-500ppm Pt ), preferably between 0.25-1.5% in relation to the total weight of silicones( ⁇ 50-300ppm Pt ). It has been observed that, when the amount of catalyst was lower than 0.1%, for the coating composition could be hardly well cured at low temperature, and the resulting coating strength was bad. When the amount of catalyst was higher than 2.5%, the hydrosilylation reaction was conducted at a fast rate, and thus impacts the pot life for application.
  • a reaction inhibitor is further added into the second coating composition, to adjust the reaction speed of hydrosilylation reaction, which is usually fast even at room temperature.
  • suitable amount of inhibitor is added into the second coating composition according to the present invention.
  • Typical hydrosilylation inhibitors that are suitable for use in the present invention are selected from alkynols and the derivatives thereof, multi alkenyl polysiloxanes, cyclic alkenyl silanes, amides, and maleates, wherein multi vinyl polysiloxane and cyclic vinyl silanes are preferred as they are more compatible with silicone rubber.
  • Suitable amount of the reaction inhibitor is about 0.5%-5.0% in relation to the total weight of silicones.
  • matting agents and/or haptic agents are further added into the second coating composition, to matt the film and make it feel smooth and slippery.
  • Typical matting agents and/or haptic agents include, but are not limited to, silicas such as fumed silica and precipitated silica, wax powders such as PE wax, PP wax, PTFE wax, and polyamide wax. These matting agents and/or haptic agents can be used alone or in combination.
  • fillers, extenders, pigments and toners can also be added into the second coating composition.
  • the addition of these materials helps to, for instance, reduce the cost, provide the coating film with desired colour effects. It should be noticed that these materials are not always necessary for the second coating composition.
  • Typical fillers and extenders include CaCO 3 , talc powder, BaSO 4 , mica powder, kaolin powder, and glass powder.
  • Typical pigments and toners include both inorganic pigments and organic pigments which are commonly used in coating industry. In order to provide the resulting coating film with a metal like visual effect or pearl like visual effect, metal powder and pearl powders can also be added into the second coating composition.
  • solvents used in the second coating composition there is no special requirement or limitation to solvents used in the second coating composition.
  • solvents used in coating and paint industry such as alcohols, ethers, esters, ketones, alkanes, aromatic hydrocarbons, or a combination there of, are suitable for use in the present invention as well.
  • a method for preparing the hybrid coating composition system according to the present invention comprises the steps of:
  • Part 1- coating in a kettle, add suitable amount of solvent and start agitation, then add resins, fillers and pigments, additives one by one during agitation at medium speed, ca.300-500 RPM, for about 10-30 minutes respectively. Raise the speed to about 2000-3000 RPM and disperse the mixture for about 1 hour, or for better dispersion, sand mill for about 10-30 minutes could be another choice.
  • the viscosity is preferably to be between 60-100KU for better dispersion, and during the agitation, cooling water may be need to cool down the mixture. If no powder is used in the system, go to next step directly.
  • Part 2 - hardener in another kettle, add suitable amount of solvent and start agitation, then add hardener resins and agitation for about 10-30minuts at medium speed, ca. 300-500 RPM. Then stop agitation and package the hardener.
  • Part 1- coating in a kettle, add suitable amount of solvent and start agitation, then add alkenyl-containing polysiloxanes, reinforcing agent, matting agents and haptic agents, fillers and pigments, additives one by one during agitation at medium speed, ca.300-500 RPM, for about 10-30 minutes respectively.
  • the viscosity is preferably to be between 60-100KU for better dispersion, and during the agitation, cooling water may be need to cool down the mixture.
  • Part 2 - hardener in another kettle, add suitable amount of solvent and start agitation, then add hydrogen methyl polysiloxanes and agitation for about 10 - 30 minutes at medium speed, ca. 300-500 RPM. Then stop agitation and package the hardener.
  • the application method of the hybrid coating composition system according to the present invention comprises the steps of:
  • hydroxyl groups is excessive because a little more hydroxyl groups is needed to react with the topcoat components. Then dilute the mixture with the above mentioned solvents to suitable viscosity.
  • the diluted coating sample could applied on the primer by methods of spray coating, brush coating, dip coating, spin coating, roll coating, curtain coating and shower coating. Spray coating is more preferred for consumer electronics and automobiles industry. Before application, the substrate maybe need some surface cleaning with alcohols or surface treatment like sanding or acid/alkali washing.
  • the curing condition is 5-30minutes at 70-100C.
  • the dry film thickness is between 5-100um, preferably 10-30um, more preferably 15-20um.
  • Mix part 1 and part 2 in ratio, for better curing the ration of alkenyl groups in part 1 to Si-H groups in part 2 is preferably to be between 1:1 to 1:3, because there are some side reactions for Si-H, and furthermore, a little more Si-H is need to react with the primer. Then dilute the mixture with the above mentioned solvents to suitable viscosity.
  • the diluted coating sample could applied on the primer by methods of spray coating, brush coating, dip coating, spin coating, roll coating, curtain coating and shower coating,
  • the curing condition could be 0.5-2 hours at 70-100C.
  • the curing condition could be 0.5-2 hours at 70-100C or 5-30 minutes at 150-180C.
  • the dry film thickness is between 10-100um, preferably 30-70um, more preferably 40-60um.
  • the hybrid coating composition system according to the present invention is suitable for use in, for example, consumer electronic devices.
  • the devices include but are not limited to mobile phones, tablets, personal computers, laptop computers, electronic readers, music players, computer accessories (monitors, mouse, keyboards, portable hard disks, printers), televisions, game consoles, global positioning system devices, and wearable devices.
  • Other applications include automotive interior and exterior parts, and home appliances.
  • Coating composition systems with silicones having different vinyl contents and hydrogen contents were prepared according to table 1, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 2.
  • Example 1 Example 2
  • Example 3 Topcoat System Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% ( ⁇ 0.2mmol/g) 100.0 N/A N/A N/A Vinyl methyl polysiloxane-50000cP, vinyl content 2 wt% ( ⁇ 0.8mmol/g) N/A 100.0 N/A N/A Vinyl methyl polysiloxane-50000cP, vinyl content 5 wt% ( ⁇ 2mmol/g) N/A N/A 100.0 N/A Vinyl methyl polysiloxane-50000cP, vinyl content 8 wt% ( ⁇ 0.32mmol/g) N/A N/A N/A 100.0 Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% ( ⁇ 5 mmol/g) 10.0 N/A N/A N/A Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.8 wt%
  • Coating composition systems with vinyl silicones and hydrogen silicones having different molecular weights or viscosities were prepared according to table 3, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 4.
  • Example 6 Example 7
  • Example 8 Topcoat Vinyl methyl polysiloxane-5000cP, vinyl content 2 wt% ( ⁇ 0.8mmol/g) 100.0 NA NA NA Vinyl methyl polysiloxane-20000cP, vinyl content 2 wt% ( ⁇ 0.8mmoi/g) NA 100.0 NA NA Vinyl methyl polysiloxane-100000cP, vinyl content 5 wt% ( ⁇ 2mmol/g) NA NA 100.0 NA Vinyl methyl polysiloxane-300000cP, vinyl content 8 wt% ( ⁇ 0.32mmol/g) NA NA NA 100.0 Hydrogen methyl polysiloxane-20cP, active hydrogen content 0.8 wt% ( ⁇ 8 mmol/g) 20.0 NA NA NA NA Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.8 wt% ( ⁇ 8 mmol/g) NA 20.0 NA NA Hydrogen methyl polysiloxane-100c
  • Coating composition systems with different reinforcing agents and dosages were prepared according to table 5, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 6.
  • Example 10 Example 11
  • Example 12 Topcoat Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% ( ⁇ 0.2mmol/g) 100.0 100.0 100.0 100.0 Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% ( ⁇ 5 mmol/g) 10.0 10.0 10.0 10.0 10.0 Reinforcing agent- fumed silica 30.0 5.0 NA NA Reinforcing agent- MQ resin NA NA 40.0 NA Reinforcing agent-Vinyl MQ resin, 1.0% vinyl NA NA NA 40.0 Inhibitor 1.5 1.5 1.5 1.5 Platinum Catalyst 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Additives: matting agent 5.0 30.0 10.0 10.0 Additives: silipery agent, wax powder 2.0 2.0 2.0 2.0 Solvents 200.0 200.0 200.0 200.0 Primer system Resins: polyester polyols 100.0 100.0 100.0 100.0 Hardeners: isocyanate 15.0
  • Coating composition systems with different platinum dosages, and primer hardener dosages were prepared according to table 7, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 8.
  • Example 16 Topcoat Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% ( ⁇ 0.2mmol/g) 100.0 100.0 100.0 100.0 Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% ( ⁇ 5 mmol/g) 10.0 10.0 10.0 10.0 10.0 Reinforcing agent- fumed silica 15.0 15.0 15.0 15.0 Inhibitor 1.5 1.5 1.5 1.5 Platinum Catalyst 0.2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Description

    Technical Field
  • This invention relates to a coating composition system for forming a complex coating structure including a primer coating layer and a top coating layer onto a substrate, specifically to a liquid silicone rubber coating composition system for forming a stain resistant and soft tactile texture complex coating structure, and its preparation method and application in consumer electrics, automobile industry and other industries.
    • Background
  • Plastics and metal materials are widely used in consumer electrics, automobile industry and other industries such as architecture. They are made into housings, cases, shells, covers, hulls of a lot of subjects like computers, phones, home appliances, automobile parts, and walls of buildings. Typical plastic materials include polycarbonate (PC), acrylonitrile butadiene styrene (ABS) copolymer, polymethyl methacrylate (PMMA), polyamide (PA), glass fibre and/or carbon fibre reinforced plastics, and soft plastic materials such as thermal plastic polyurethane (TPU), etc. Typical metals substrates include aluminium, steel, anodized aluminium oxide (AAO), aluminium-magnesium alloy, etc. The materials as a substrate usually need to be covered with a coating for better property or additional protection. For example, coatings with tactile texture are required by customers in many industries.
  • Soft resins have been used as the main material in coating compositions to provide the resulting coatings with soft tactile texture. Typical soft resins include polyester polyols, polyurethane polyols, polyurethane dispersions, acrylic latex etc. The soft resin system may be solvent based or water based. For example, WO201289827 discloses a polyurethane soft touch coating composition characterized in that it comprises the reaction product of (A) a non-hydrolysable polyol binder, and (B) an organic polyisocyanate.
  • Elastic powders have been also used in coating compositions to provide the resulting coatings with soft feel and matting effects. Typical elastic powders include silicone rubber powders or microspheres, microspheres of expansible materials, etc. for example, US20060021888 discloses a coating composition wherein silicone rubber particles are added to a traditional resin coating system to obtain a coating with soft tactile texture and antiglare effects.
  • By including soft resins or elastic powders, the coatings are provided with soft tactile texture and thus have been widely used in the coating industry. Due to their poor stain resistance property, however, the practical application has been limited. Especially for applications on dark color substrates, it is normally impractical to use coatings with soft resins or elastic powders, as stain marks are more obvious in a dark color background.
  • There have been approaches to improve the stain resistant performance of a traditional soft tactile texture coating. US20070137524 discloses a new resin system of polybutadiene polyol and polyolefinic acid. It is used in soft feel coating compositions, to increase discoloration resistance, heat resistance, yellowing resistance and anti-fouling properties of the resulting coatings. Although the composition achieves better performance upon modifications, the stain resistance of the resulting coatings is still not satisfactory.
  • Among different coatings, silicone rubber coatings are frequently used in varies of industries, due to their good electric insulation, physical strength and elasticity, soft feel, stain resistance etc. The silicone rubber systems are mainly based on two reaction mechanisms: condensation reaction and addition reaction. The former is a reaction between hydroxyl silicone oils with different silanes, and the latter is a reaction between vinyl silicone oils with active hydrogen silicone oils. Both of the two silicone rubber systems are widely used in coating industry.
  • CN1036279 discloses a colourful silicone elastic coating for optical fiber protection and label materials for ceramic and metals. The composition comprises methyl vinyl polysiloxane, vinyl MQ reinforcing agent, organohydrogenpolysiloxane, platinum catalyst, stabilizer, and pigments. Based on a thermal cure system, the coating composition requires a curing temperature as high as from 430 °C to 480 °C.
  • Silicone rubbers may also be used for fabrics, textiles and leathers because of their heat and weather resistance, water repellence, softness, cohesion, flexibility, etc. EP2009059 discloses a liquid silicone rubber coating composition for curtain airbags. The coating coating composition comprising (A) an organopolysiloxane containing silicon bonded alkenyl radicals, (B) an organohydrogenpolysiloxane containing Si-H radicals, (C) an addition reaction catalyst, (D) finely divided silica, (E) an organosilicon compound containing epoxy and alkoxy radicals, (F) an organic titanium, zirconium or aluminum compound, and (G) a silanol-_containing silane or siloxane compound is coated on a surface of an airbag base fabric and cured to form a rubber coating layer thereon.
  • However, there have been technical issues regarding stain resistant property and soft tactile texture of silicone rubber coatings. In some occasions, coatings need to have both good stain resistant property and soft tactile texture, but this can hardly be achieved with existing silicone rubber formulations, as soft tactile texture normally reduces stain resistant property. Another technical issue of silicone rubber coatings is the adhesion to different substrates. Especially for specific substrate materials like plastics and metals, normal silicone rubber coatings are known to have poor adhesion, and thus are limited in practical use.
  • JP2005296697A discloses a tactile coating on a substrate formed using a primer layer of a hydrosilylation cure silicone and a top layer of a polyurethane or silicone hydrosilylation curing polymer.
    • Description of the Invention
  • The present invention provides for an article coated with a coating composition system in accordance with claim 1 suitable for forming a stain resistant and soft tactile texture coating onto a variety of substrate materials including plastic materials, metal materials, ceramic materials, and concrete materials. The coating composition system can be cured under mild curing conditions, and provide the resulting coating with excellent properties in terms of adhesion to the substrates, strength, and abrasion resistance. The present invention also provides for a method tor forming a stain resistant and soft tactile coating system onto a substrate in accordance with claim 10, as well as the specific articles comprising the coating in accordance with claim 11.
  • According to the present invention, the coating composition system comprises two separate coating compositions, wherein the first coating composition is to form a primer coating onto a substrate, and the second coating composition is to form a top coating onto the primer coating. The primer coating serves as a middle layer between the substrate and top coating film, to improve the adhesion of the coating layers to the substrate. During application, the first composition is applied onto a substrate and cured to form a primer coating, the second coating composition is consequently applied onto the primer coating and cured to form a top coating.
  • The first coating composition according to the present invention includes: a hydroxyl resin, a hardener resin having functional groups which react with hydroxyl groups of the hydroxyl resin, an optional catalyst for the reaction between the resins, an optional adhesion promoter, optional additives, fillers, extenders, pigments and toners.
  • One or more resins with hydroxyl groups are used as the main ingredient of the first coating composition. Typical resins that are suitable for use in the present invention include alkyd resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, and modified silicone resins. The resins can be used alone or in combination.
  • In addition to the hydroxyl resins, the first coating composition comprises one or more hardener resins having functional groups which react with the hydroxyl resins. Typical resins that are suitable for use in the present invention include amino resins, isocyanates, and melamine resins. Typically the hardener resins are selected from poly-isocyanates, dimer-isocyanates, trimer-isocyanates, and biuret- isocyanates. The hardener resins can be used alone or in combination.
  • In accordance with the present invention, the molar ratio of hydroxyl groups of the hydroxyl resin is excessive over the molar ratio of the functional groups of the hardener resin in the first composition. When the first coating composition is in contact with the second coating composition which will be discussed in later part of the description, the excessive hydroxyl groups may further react with other functional groups in the second coating composition, such as Si-H groups, as shown below:

            ~~Si-H + HO-R → ~~Si-O-R + H2

    The reaction between the excessive hydroxyl groups of the first coating composition and the other functional groups in the second coating composition helps to improve the adhesion between coating layers and the substrate.
  • Different catalysts may be added into the first coating composition, to facilitate the reaction between the resins. The catalysts are selected according to the resin system used in the first coating composition. Typical catalysts that are suitable for use in the present invention include organic cobalt catalysts and manganese catalysts for alkyd resins, organic tin catalysts for polyurethane resins.
  • Adhesion promoters are added into the first coating composition to enhance the adhesion between the coating layers and the substrate. Typical adhesion promoters that are suitable for use in the present invention include silanes with functional groups, such as epoxy silanes, amino silanes, and alkenyl silanes; organic metal compounds, such as titanates, zirconates, aluminates; resins with a hydroxyl value of from 100 mgKOH/g to 300 mgKOH/g, an acid value of from 20 mgKOH/g to 200mgKOH/g, or phosphate resins.
  • According to one embodiment of the present invention, different additives can be further added into the first coating composition, such as levelling agent, defoaming agent etc. As a preferred option, fillers, extenders, pigments and toners can also be added into the first coating composition. The addition of these materials helps to, for instance, reduce the cost, provide the coating film with desired colour effects. It should be noticed that these materials are not necessarily added into the first coating composition. Typical fillers and extenders include CaCO3, talc powder, BaSO4, mica powder, kaolin powder, and glass powder. Typical pigments and toners include both inorganic pigments and organic pigments which are commonly used in coating industry. In order to provide the resulting coating film with a metal like visual effect or pearl like visual effect, metal powder and pearl powders can also be added into the first coating composition.
  • There is no special requirement or limitation to solvents used in the first coating composition. Generally, solvents used in coating and paint industry, such as alcohols, ethers, esters, ketones, alkanes, aromatic hydrocarbons, or a combination there of, are suitable for use in the present invention as well.
  • The second coating composition according to the present invention includes: an alkenyl containing polysiloxane of defined alkenyl content, a Si-H bond containing polysiloxane, a hydrosilylation catalyst, an optional reinforcing agent, an optional reaction inhibitor, optional matting agents, haptic agents, fillers, extenders, and pigments.
  • The curing mechanism of the second coating composition is based on an addition reaction curing process, wherein hydrosilylation takes place between the alkenyl groups of the alkenyl containing polysiloxane and the Si-H groups of the Si-H bond containing polysiloxane, at the presence of an organic precious metal catalyst.
  • The alkenyl containing polysiloxane suitable for use in the present invention is shown as the formula (I) below
    Figure imgb0001
     wherein R represents an alkyl group having 1 ~ 8 carbon atoms, or an alkenyl group having 2 ~ 10 carbon atoms, which may be selected from, for example, methyl, ethyl, butyl, phenyl, etc., and vinyl, allyl, buyenyl, pentenyl, hexenyl, heptenyl, etc., preferably R is methyl or vinyl; R1 and R3 each independently represents an alkyl group having 1~ 8 carbon atoms, which may be selected from, for example, methyl, ethyl, butyl, phenyl, etc., preferably R1 and R3 are methyl; R2 represents an alkenyl group having 2 ~ 10 carbon atoms, which may be selected from, for example, vinyl, allyl, buyenyl, pentenyl, hexenyl, heptenyl groups, etc., preferably R2 is vinyl group; the sum of l+m+n+a is not less than 200, preferably not less than 500, and meanwhile the sum of l+m+n+a is not greater than 5000, preferably not greater than 2000.
  • In a further embodiment of the present invention, the alkenyl containing polysiloxane is selected such that the viscosity of the alkenyl containing polysiloxane is not less than 1000 Cp at 25°C, preferably not less than 5,000 Cp at 25 °C, and meanwhile not greater than -500,000Cp at 25°C, preferably not greater than 100,000 cP at 25°C. Unless otherwise specified, said viscosity of the alkenyl containing polysiloxane is measured according to ASTM D2225. It has been observed that alkenyl containing polysiloxanes within the defined ranges helped to improve the strength of resulting coatings. In accordance with the present invention, the alkenyl containing polysiloxane is selected such that the alkenyl content is not less than 0.2mmol/g, and meanwhile, not greater than 5.0mmol/g, preferably not greater than 3.0 mmol/g. It has been observed that alkenyl containing polysiloxanes within the defined ranges helped to improve the strength and tactile texture of the resulting coatings. Specifically, alkenyl containing polysiloxanes with an alkenyl content lower than 0.02mmol/g resulted in soft coating layers with poor strength, and alkenyl containing polysiloxanes with an alkenyl content higher than 5.0mmol/g resulted in hard coating layers with little soft feel and tactile texture.
  • The Si-H bond containing polysiloxane suitable for use in the present invention is shown as the formula (II) below
    Figure imgb0002
    • wherein R4 and R5 each independently represents an alkyl group having 1 ~ 8 carbon atoms, which may be selected from, for example, methyl, ethyl, butyl, phenyl, etc., preferably R4 and R5 are methyl; R6 represents an alkyl group having 1 ~ 8 carbon atoms, or H; the sum of o+p+q+b is not less than 5, and not greater than 500;
    • In a further embodiment of the present invention, the Si-H bond containing polysiloxane is selected such that its viscosity is not less than 10 cP at 25°C, preferably not less than 20 cP at 25 °C, and meanwhile not greater than 1000 cP at 25 °C, preferably not greater than 500 cP at 25°C. It has been observed that Si-H bond containing polysiloxanes out of the defined range could hardly provide the resulting coatings with satisfying strength. In another embodiment of the present invention, Si-H bond containing polysiloxane is selected such that its active hydrogen content is not less than 1.0mmol/g, preferably not less than 5mmol/g, and meanwhile not greater than 16.0mmol/g, preferably not greater than 10mmol/g. It has been observed that Si-H bond containing polysiloxanes with an active hydrogen content lower than 1 .0mmol/g resulted in soft coating layers with poor strength, and that Si-H bond containing polysiloxanes with an active hydrogen content higher than 16.0mmol/g resulted in brittle coating layers with poor strength.
  • According to one embodiment of the present invention, a reinforcing agent is added into the second coating composition to further enhance the strength of resulting coatings. Generally, the reinforcing agent selected from one or more of the group consisting of silica, mono-functional auad-functional silicone resins (MQ silicone resins), polyhedral oligomeric silsesquioxane (POSS), carbon black, and fibers.
  • As an option, any silica material containing SiO2 can be used as the reinforcing agent of the second coating composition according to the present invention. Preferably the silica material is selected from fumed silica, precipitated silica and quartz powders, which can be used alone or in combination. More preferably silica material is selected from fumed silicas which have gone through surface treatment with silanes. In a further embodiment of the present invention, the silica material is selected such that its BET surface area is between 500-400m2/g, preferably between 150-300m2/g, its primary particle size is between 5-50nm, and its average particle size is below 20um, preferably below 10um.
  • MQ silicone resins may also be added as the reinforcing agent into the second coating composition. When used herein, MQ silicone resins are meant to represent a broad range of hydrolytic condensation products of mono-functional silane (M) and Quad-functional silane (Q). Due to their three-dimensional network structure, MQ silicone resins may provide the resulting coatings with outstanding properties such as high hardness, antifriction, weathering ageing resistance, and may help reinforce the resulting coatings. There is no special requirement or limitation to MQ resins for use as the reinforcing agent in the second coating composition according to the present invention, yet MQ resins with alkenyl groups and active hydrogen groups are preferred.
  • As another option, reinforcing agents like POSS, carbon black, and fibers may also be used alone or in combination with the above mentioned silica materials and MQ silicone resins as the reinforcing agent in the second coating composition according to the present invention.
  • To facilitate the hydrosilylation reaction between the alkenyl containing polysiloxane and the Si-H bond containing polysiloxane, addition reaction catalyst is further added into the second composition. According to the present invention, the addition reaction catalyst is not particularly limited as long as it promotes hydrosilylation reaction between an alkenyl group and a Si-H group. Typical catalysts that are suitable for use in the present invention are selected from, but not limited to, platinum compounds, palladium compounds, rhodium compounds, and ruthenium compounds, wherein platinum compounds are preferred. In order to make the film to cure well at mild conditions, for instance, 0.5-2.0 hours at 70-100°C, an effective amount of the catalyst is between 0.1% to 2.5% in relation to the total weight of silicones(~20-500ppm Pt ), preferably between 0.25-1.5% in relation to the total weight of silicones(~ 50-300ppm Pt ). It has been observed that, when the amount of catalyst was lower than 0.1%, for the coating composition could be hardly well cured at low temperature, and the resulting coating strength was bad. When the amount of catalyst was higher than 2.5%, the hydrosilylation reaction was conducted at a fast rate, and thus impacts the pot life for application.
  • According to one embodiment of the present invention, a reaction inhibitor is further added into the second coating composition, to adjust the reaction speed of hydrosilylation reaction, which is usually fast even at room temperature. In order to prolong the pot life of the second coating composition, suitable amount of inhibitor is added into the second coating composition according to the present invention. Typical hydrosilylation inhibitors that are suitable for use in the present invention are selected from alkynols and the derivatives thereof, multi alkenyl polysiloxanes, cyclic alkenyl silanes, amides, and maleates, wherein multi vinyl polysiloxane and cyclic vinyl silanes are preferred as they are more compatible with silicone rubber. Suitable amount of the reaction inhibitor is about 0.5%-5.0% in relation to the total weight of silicones.
  • According to one embodiment of the present invention, matting agents and/or haptic agents are further added into the second coating composition, to matt the film and make it feel smooth and slippery. Typical matting agents and/or haptic agents include, but are not limited to, silicas such as fumed silica and precipitated silica, wax powders such as PE wax, PP wax, PTFE wax, and polyamide wax. These matting agents and/or haptic agents can be used alone or in combination.
  • According to one embodiment of the present invention, fillers, extenders, pigments and toners can also be added into the second coating composition. The addition of these materials helps to, for instance, reduce the cost, provide the coating film with desired colour effects. It should be noticed that these materials are not always necessary for the second coating composition. Typical fillers and extenders include CaCO3, talc powder, BaSO4, mica powder, kaolin powder, and glass powder. Typical pigments and toners include both inorganic pigments and organic pigments which are commonly used in coating industry. In order to provide the resulting coating film with a metal like visual effect or pearl like visual effect, metal powder and pearl powders can also be added into the second coating composition.
  • There is no special requirement or limitation to solvents used in the second coating composition. Generally, solvents used in coating and paint industry, such as alcohols, ethers, esters, ketones, alkanes, aromatic hydrocarbons, or a combination there of, are suitable for use in the present invention as well.
  • In another aspect of the present invention, a method for preparing the hybrid coating composition system according to the present invention is provided, which comprises the steps of:
    • Preparation of the first coating composition
  • Part 1- coating: in a kettle, add suitable amount of solvent and start agitation, then add resins, fillers and pigments, additives one by one during agitation at medium speed, ca.300-500 RPM, for about 10-30 minutes respectively.
    Raise the speed to about 2000-3000 RPM and disperse the mixture for about 1 hour, or for better dispersion, sand mill for about 10-30 minutes could be another choice. The viscosity is preferably to be between 60-100KU for better dispersion, and during the agitation, cooling water may be need to cool down the mixture. If no powder is used in the system, go to next step directly.
  • After dispersion or sand milling, low the speed to about 300-500 RPM and add the catalyst and residual solvents one by one during agitation and agitate for 10-30 minutes respectively. Then stop agitation and package the coating.
  • Part 2 - hardener: in another kettle, add suitable amount of solvent and start agitation, then add hardener resins and agitation for about 10-30minuts at medium speed, ca. 300-500 RPM. Then stop agitation and package the hardener.
    • Preparation of the second coating composition
  • Part 1- coating: in a kettle, add suitable amount of solvent and start agitation, then add alkenyl-containing polysiloxanes, reinforcing agent, matting agents and haptic agents, fillers and pigments, additives one by one during agitation at medium speed, ca.300-500 RPM, for about 10-30 minutes respectively.
  • Then raise the speed to about 2000-3000 RPM and disperse the mixture for about 1 hour, or for better dispersion, sand mill for about 10-30 minutes could be another choice. The viscosity is preferably to be between 60-100KU for better dispersion, and during the agitation, cooling water may be need to cool down the mixture.
  • After dispersion or sand milling, low the speed to about 300-500 RPM and add the inhibitors, catalyst and residual solvents one by one during agitation and agitate for 10-30 minutes respectively. Then stop agitation and package the coating.
  • Part 2 - hardener: in another kettle, add suitable amount of solvent and start agitation, then add hydrogen methyl polysiloxanes and agitation for about 10 - 30 minutes at medium speed, ca. 300-500 RPM. Then stop agitation and package the hardener.
  • In another aspect of the present invention, the application method of the hybrid coating composition system according to the present invention is provided, which comprises the steps of:
    • Application of the first coating composition
  • Mix part 1 and part 2 in ratio, hydroxyl groups is excessive because a little more hydroxyl groups is needed to react with the topcoat components. Then dilute the mixture with the above mentioned solvents to suitable viscosity. The diluted coating sample could applied on the primer by methods of spray coating, brush coating, dip coating, spin coating, roll coating, curtain coating and shower coating. Spray coating is more preferred for consumer electronics and automobiles industry. Before application, the substrate maybe need some surface cleaning with alcohols or surface treatment like sanding or acid/alkali washing.
  • Put the coated parts in the oven, the curing condition is 5-30minutes at 70-100C.
  • The dry film thickness is between 5-100um, preferably 10-30um, more preferably 15-20um.
    • Application of the second coating composition
  • Mix part 1 and part 2 in ratio, for better curing the ration of alkenyl groups in part 1 to Si-H groups in part 2 is preferably to be between 1:1 to 1:3, because there are some side reactions for Si-H, and furthermore, a little more Si-H is need to react with the primer. Then dilute the mixture with the above mentioned solvents to suitable viscosity. The diluted coating sample could applied on the primer by methods of spray coating, brush coating, dip coating, spin coating, roll coating, curtain coating and shower coating,
  • Put the coated parts in the oven, for plastic substrates, the curing condition could be 0.5-2 hours at 70-100C. For metal substrates, the curing condition could be 0.5-2 hours at 70-100C or 5-30 minutes at 150-180C.
  • The dry film thickness is between 10-100um, preferably 30-70um, more preferably 40-60um.
  • In yet another aspect of the present invention, uses of the hybrid coating composition system according to the present invention are provided. The hybrid coating composition system according to the present invention is suitable for use in, for example, consumer electronic devices. Specifically, the devices include but are not limited to mobile phones, tablets, personal computers, laptop computers, electronic readers, music players, computer accessories (monitors, mouse, keyboards, portable hard disks, printers), televisions, game consoles, global positioning system devices, and wearable devices. Other applications include automotive interior and exterior parts, and home appliances.
    • Examples
  • The invention will be elucidated with reference to the following examples. These are intended to illustrate the invention but are not to be construed as limiting in any manner the scope thereof.
  • In the following examples, formulation changes in terms of content of functional groups, molecular weight, reinforcing agents, amount of catalyst, were tested and the results were shown below.
    • Examples 1-4: test of vinyl content and active hydrogen content of silicone
  • Coating composition systems with silicones having different vinyl contents and hydrogen contents were prepared according to table 1, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 2. Table 1 Examples to study the Impact of vinyl content and active hydrogen content of silicone
    Example 1 Example 2 Example 3 Example 4
    Topcoat System
    Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% (~0.2mmol/g) 100.0 N/A N/A N/A
    Vinyl methyl polysiloxane-50000cP, vinyl content 2 wt% (~0.8mmol/g) N/A 100.0 N/A N/A
    Vinyl methyl polysiloxane-50000cP, vinyl content 5 wt% (~2mmol/g) N/A N/A 100.0 N/A
    Vinyl methyl polysiloxane-50000cP, vinyl content 8 wt% (~0.32mmol/g) N/A N/A N/A 100.0
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% (~5 mmol/g) 10.0 N/A N/A N/A
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.8 wt% (~8 mmol/g) N/A 20.0 N/A N/A
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 1.6 wt% (~16 mmol/g) N/A NA 30.0 50.0
    Reinforcing agent- fumed silica 15.0 15.0 15.0 15.0
    Inhibitor 1.5 2.0 2.0 2.0
    Platinum Catalyst 1.0 1.0 1.0 1.0
    Additives: matting agent 10.0 10.0 10.0 10.0
    Additives: slippery agent, wax powder 2.0 2.0 2.0 2.0
    Solvents 200.0 200.0 200.0 200.0
    Primer system
    Resins: polyester polyols 100.0 100.0 100.0 100.0
    Hardeners: isocyanate 15.0 15.0 15.0 15.0
    Adhesion promoters/resins 20.0 20.0 20.0 20.0
    Catalyst: Tin compound 1.0 1.0 1.0 1.0
    Additives 1.0 1.0 1.0 1.0
    Solvents 150.0 150.0 150.0 150.0
    Table 2 Test results of Example 1-4
    Example 1 Example 2 Example 3 Example 4
    Appearance Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery
    Cross-cut Adhesion, ASTM 3359; 1.0mmX1.0mm 5B 5B 5B 5B
    Abrasion-RCA Pass Pass Pass Pass
    175g, 250cycles
    Abrasion-Alcohol Pass Pass Pass Pass
    250g, 250 rubs
    MEK resistance, 23°C,3minutes Pass Pass Pass Pass
    Hot water resistance,0.5 hour at 95 °C Pass Pass Pass Pass
    Humidity/Temperature test, 80C,95%RH,96 hours Pass Pass Pass Pass
    Thermal shock,-40°C/50% and 85°C/75% Pass Pass Pass Pass
    48 cycles, 4 days
    QUV, ASTM G154 UVA-340, 0.71W/m2/nm ultraviolet lamp and 60°C, 96 hours Pass Pass Pass Pass
    Impact resistance, 1kg, 50cm Pass Pass Pass Pass
    Artificial sweat resistance Pass Pass Pass Pass
    Permanent mark pen,1 hour at 23 °C Pass Pass Pass Pass
    Cosmetics-Foundation cream Pass Pass Pass Pass
    Cosmetics-Lipstick Pass Pass Pass Pass
    Cosmetics-hand cream,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-sunscreen lotion,1 hour at 23°C Pass Pass Pass Pass
    Coffee, 1 hour at 23°C Pass Pass Pass Pass
    Beer,1 hour at 23°C Pass Pass Pass Pass
    Red wine,1 hour at 23°C Pass Pass Pass Pass
    Mustard,1 hour at 23°C Pass Pass Pass Pass
    Ketchup,1 hour at 23°C Pass Pass Pass Pass
    Coca-cola,1 hour at 23°C Pass Pass Pass Pass
    Olive Oil,1 hour at 23°C Pass Pass Pass Pass
    • Examples 5-8, test of Mw and/or viscosity of vinyl silicone and hydrogen silicone
  • Coating composition systems with vinyl silicones and hydrogen silicones having different molecular weights or viscosities were prepared according to table 3, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 4. Table 3 Examples to study the Impact of Mw or viscosity of vinyl silicone and hydrogen silicone
    Example 5 Example 6 Example 7 Example 8
    Topcoat
    Vinyl methyl polysiloxane-5000cP, vinyl content 2 wt% (~0.8mmol/g) 100.0 NA NA NA
    Vinyl methyl polysiloxane-20000cP, vinyl content 2 wt% (~0.8mmoi/g) NA 100.0 NA NA
    Vinyl methyl polysiloxane-100000cP, vinyl content 5 wt% (~2mmol/g) NA NA 100.0 NA
    Vinyl methyl polysiloxane-300000cP, vinyl content 8 wt% (~0.32mmol/g) NA NA NA 100.0
    Hydrogen methyl polysiloxane-20cP, active hydrogen content 0.8 wt% (~8 mmol/g) 20.0 NA NA NA
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.8 wt% (~8 mmol/g) NA 20.0 NA NA
    Hydrogen methyl polysiloxane-100cP, active hydrogen content 0.8 wt% (~8 mmol/g) NA NA 20.0 NA
    Hydrogen methyl polysiloxane-500cP, active hydrogen content 0.8 wt% (~8 mmol/g) NA NA NA 20.0
    Reinforcing agent- fumed silica 15.0 15.0 15.0 15.0
    Inhibitor 2.0 2.0 2.0 2.0
    Platinum Catalyst 1.0 1.0 1.0 1.0
    Additives: matting agent 10.0 10.0 10.0 10.0
    Additives: silipery agent, wax powder 2.0 2.0 2.0 2.0
    Solvents 200.0 200.0 200.0 200.0
    Primer system
    Resins: polyester polyols 100.0 100.0 100.0 100.0
    Hardeners: isocyanate 15.0 15.0 15.0 15.0
    Adhesion promoters/resins 20.0 20.0 20.0 20.0
    Catalyst: Tin compound 1.0 1.0 1.0 1.0
    Additives 1.0 1.0 1.0 1.0
    Solvents 150.0 150.0 150.0 150.0
    Table 4 Test results of Example 5-8
    Example 5 Example 6 Example 7 Example 8
    Appearance Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery
    Cross-cut Adhesion, ASTM 3359; 1.0mmX1.0mm 5B 5B 5B 5B
    Abrasion-RCA Pass Pass Pass Pass
    175g, 250cycles
    Abrasion-Alcohol Pass Pass Pass Pass
    250g, 250 rubs
    MEK resistance, 23°C,3minutes Pass Pass Pass Pass
    Hot water resistance,0.5 hour at 95 C Pass Pass Pass Pass
    Humidity/Temperature test, 80°C,95%RH,96 hours Pass Pass Pass Pass
    Thermal shock,-40°C/50% and 85°C/75% Pass Pass Pass Pass
    48 cycles, 4 days
    QUV, ASTM G154 UVA-340, 0.71W/m2/nm ultraviolet lamp and 60°C, 96 hours Pass Pass Pass Pass
    Impact resistance, 1kg, 50cm Pass Pass Pass Pass
    Artificial sweat resistance Pass Pass Pass Pass
    Permanent mark pen,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-Foundation cream Pass Pass Pass Pass
    Cosmetics-Lipstick Pass Pass Pass Pass
    Cosmetics-hand cream,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-sunscreen lotion,1 hour at 23°C Pass Pass Pass Pass
    Coffee,1 hour at 23°C Pass Pass Pass Pass
    Beer,1 hour at 23°C Pass Pass Pass Pass
    Red wine,1 hour at 23°C Pass Pass Pass Pass
    Mustard,1 hour at 23°C Pass Pass Pass Pass
    Ketchup,1 hour at 23°C Pass Pass Pass Pass
    Coca-cola,1 hour at 23°C Pass Pass Pass Pass
    Olive Oil,1 hour at 23°C Pass Pass Pass Pass
    • Examples 9-12 test of reinforcing agent and matting silica
  • Coating composition systems with different reinforcing agents and dosages were prepared according to table 5, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 6. Table 5 Examples to study the impact of reinforcing agent and matting silica
    Example 9 Example 10 Example 11 Example 12
    Topcoat
    Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% (~0.2mmol/g) 100.0 100.0 100.0 100.0
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% (~5 mmol/g) 10.0 10.0 10.0 10.0
    Reinforcing agent- fumed silica 30.0 5.0 NA NA
    Reinforcing agent- MQ resin NA NA 40.0 NA
    Reinforcing agent-Vinyl MQ resin, 1.0% vinyl NA NA NA 40.0
    Inhibitor 1.5 1.5 1.5 1.5
    Platinum Catalyst 1.0 1.0 1.0 1.0
    Additives: matting agent 5.0 30.0 10.0 10.0
    Additives: silipery agent, wax powder 2.0 2.0 2.0 2.0
    Solvents 200.0 200.0 200.0 200.0
    Primer system
    Resins: polyester polyols 100.0 100.0 100.0 100.0
    Hardeners: isocyanate 15.0 15.0 15.0 15.0
    Adhesion promoters/resins 20.0 20.0 20.0 20.0
    Catalyst: Tin compound 1.0 1.0 1.0 1.0
    Additives 1.0 1.0 1.0 1.0
    Solvents 150.0 150.0 150.0 150.0
    Table 6 Test results of Example 9-12
    Example 9 Example 10 Example 11 Example 12
    Appearance Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery
    Cross-cut Adhesion, ASTM 3359; 1.0mmX1.0mm 5B 5B 5B 5B
    Abrasion-RCA Pass Pass Pass Pass
    175g, 250cycles
    Abrasion-Alcohol Pass Pass Pass Pass
    250g, 250 rubs
    MEK resistance, 23°C ,3minutes Pass Pass Pass Pass
    Hot water resistance,0.5 hour at 95 C Pass Pass Pass Pass
    Humidity/Temperature test, 80C,95%RH,96 hours Pass Pass Pass Pass
    Thermal shock,-40°C/50% and 85°C/75% Pass Pass Pass Pass
    48 cycles, 4 days
    QUV, ASTM G154 UVA-340, 0.71W/m2/nm ultraviolet lamp and 60°C, 96 hours Pass Pass Pass Pass
    Impact resistance, 1kg, 50cm Pass Pass Pass Pass
    Artificial sweat resistance Pass Pass Pass Pass
    Permanent mark pen,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-Foundation cream Pass Pass Pass Pass
    Cosmetics-Lipstick Pass Pass Pass Pass
    Cosmetics-hand cream,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-sunscreen lotion,1 hour at 23°C Pass Pass Pass Pass
    Coffee, 1 hour at 23°C Pass Pass Pass Pass
    Beer,1 hour at 23°C Pass Pass Pass Pass
    Red wine,1 hour at 23°C Pass Pass Pass Pass
    Mustard,1 hour at 23°C Pass Pass Pass Pass
    Ketchup,1 hour at 23°C Pass Pass Pass Pass
    Coca-cola,1 hour at 23°C Pass Pass Pass Pass
    Olive Oil,1 hour at 23°C Pass Pass Pass Pass
    • Examples 13 - 16 test of platinum catalyst and primer.
  • Coating composition systems with different platinum dosages, and primer hardener dosages were prepared according to table 7, respectively. They were applied onto a substrate of polycarbonate and acrylonitrile butadiene styrene copolymer, and then cured for further tests. It was seen that the listed formulas all achieved good test results, see table 8. Table 7 Examples to study the impact of platinum catalyst and primer
    Example 13 Example 14 Example 15 Example 16
    Topcoat
    Vinyl methyl polysiloxane-50000cP, vinyl content 0.5 wt% (~0.2mmol/g) 100.0 100.0 100.0 100.0
    Hydrogen methyl polysiloxane-50cP, active hydrogen content 0.5 wt% (~5 mmol/g) 10.0 10.0 10.0 10.0
    Reinforcing agent- fumed silica 15.0 15.0 15.0 15.0
    Inhibitor 1.5 1.5 1.5 1.5
    Platinum Catalyst 0.2 1.0 1.0 1.0
    Additives: matting agent 10.0 10.0 10.0 10.0
    Additives: slippery agent, wax powder 2.0 2.0 2.0 2.0
    Solvents 200.0 200.0 200.0 200.0
    Primer system
    Resins: polyester polyols 100.0 100.0 100.0 100.0
    Hardeners: isocyanate 15.0 10.0 30.0 15.0
    Adhesion promoters/resins 20.0 20.0 20.0 30.0
    Catalyst: Tin compound 1.0 1.0 1.0 1.0
    Additives 1.0 1.0 1.0 1.0
    Solvents 150.0 150.0 150.0 150.0
    Table 8 Test results of Example 13-16
    Example 13 Example 14 Example 15 Example 16
    Appearance Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery Low gloss, soft feel, smooth and slippery
    Cross-cut Adhesion, ASTM 3359; 1.0mmX1.0mm 5B 5B 5B 5B
    Abrasion-RCA Pass Pass Pass Pass
    175g, 250cycles
    Abrasion-Alcohol Pass Pass Pass Pass
    250g, 250 rubs
    MEK resistance, 23°C,3minutes Pass Pass Pass Pass
    Hot water resistance,0.5 hour at 95 °C Pass Pass Pass Pass
    Humidity/Temperature test, 80C,95%RH, 96 hours Pass Pass Pass Pass
    Thermal shock,-40°C/50% and 85°C/75% Pass Pass Pass Pass
    48 cycles, 4 days
    QUV, ASTM G154 UVA-340, 0.71W/m2/nm ultraviolet lamp and 60°C, 96 hours Pass Pass Pass Pass
    Impact resistance, 1kg, 50cm Pass Pass Pass Pass
    Artificial sweat resistance Pass Pass Pass Pass
    Permanent mark pen,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-Foundation cream Pass Pass Pass Pass
    Cosmetics-Lipstick Pass Pass Pass Pass
    Cosmetics-hand cream,1 hour at 23°C Pass Pass Pass Pass
    Cosmetics-sunscreen lotion,1 hour at 23°C Pass Pass Pass Pass
    Coffee, 1 hour at 23°C Pass Pass Pass Pass
    Beer,1 hour at 23°C Pass Pass Pass Pass
    Red wine,1 hour at 23°C Pass Pass Pass Pass
    Mustard,1 hour at 23°C Pass Pass Pass Pass
    Ketchup,1 hour at 23°C Pass Pass Pass Pass
    Coca-cola,1 hour at 23°C Pass Pass Pass Pass
    Olive Oil,1 hour at 23°C Pass Pass Pass Pass

Claims (11)

  1. An article coated with a coating composition system for forming a stain resistant and soft tactile texture coating, which includes:
    a primer layer formed from a first composition comprising:
    a hydroxyl resin selected from one or more of the group consisting of alkyd resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, and modified silicone resins;
    a hardener resin having functional groups which react with hydroxyl groups of the hydroxyl resin;
    wherein the molar ratio of hydroxyl groups of the hydroxyl resin is excessive over the molar ratio of the functional groups of the hardener; and
    a topcoat layer on the primer layer, which topcoat layer is formed from a second composition comprising:
    an alkenyl containing polysiloxane of formula (I)
    Figure imgb0003
     wherein
    R represents an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
    R1 and R3 each independently represents an alkyl group having 1 to 8 carbon atoms;
    R2 represents an alkenyl group having 2 to 10 carbon atoms;
    l+m+n+a is within the range from 200 to 15000;
    wherein the alkenyl content of the alkenyl-containing polysiloxane is not less than 0.2 mmol/g and not greater than 5.0 mmol/g,
    a Si-H bond containing polysiloxane of formula (II)
    Figure imgb0004
     wherein
    R4 and R5 each independently represents an alkyl group having 1 to 8 carbon atoms;
    R6 represents an alkyl group having 1 to 8 carbon atoms, or H;
    o+p+q+b is within the range from 5 to 500;
    a catalyst selected from one or more of the group consisting of platinum compounds, palladium compounds, rhodium compounds and ruthenium compounds.
  2. The coated article according to claim 1, wherein the hardener of the first composition is selected from one or more of the group consisting of amino resins, isocyanates, and melamine resins.
  3. The coated article according to any one of claims 1-2, wherein the first composition further comprises a catalyst selected from one or more of the group consisting of organic cobalt catalysts, manganese catalysts, and organic tin catalysts.
  4. The coated article according to claim 3, wherein the amount of the catalyst in the first composition is within the range from 0 to 2.5 wt% in relation to the total weight of the hydroxyl resin.
  5. The coated article according to any one of claims 1-4, wherein the first composition further comprises an adhesion promoter selected from one or more of the group consisting of epoxy silanes, amino silanes, alkenyl silanes, titanate, zirconate, aluminate, polymers with a hydroxyl value of from 100 to 300 mgKOH/g or an acid value of from 20 to 200 mgKOH/g.
  6. The coated article according to any one of claims 1-5, wherein the amount of the catalyst in the second composition is within the range from 0.1 to 2.5 wt% in relation to the total weight of the alkenyl containing polysiloxane and the Si-H bond containing polysiloxane.
  7. The coated article according to any one of claims 1-6, wherein the second composition further comprises a hydrosilylation inhibitor selected from one or more of the group consisting of alkynols and their derivatives, multi-alkenyl polysiloxanes, cyclic alkenyl silanes, amides, and maleates.
  8. The coated article according to claim 7, wherein the amount of the hydrosilylation inhibitor is within the range from 0 to 5.0 wt% in relation to the total weight of the alkenyl containing polysiloxane and the Si-H bond containing polysiloxane.
  9. The coated article according to any one of claims 1-8, wherein the second composition further comprises a reinforcing agent selected from one or more of the group consisting of silica, mono-functional quad-functional silicone resins, polyhedral oligomeric silsesquioxane, carbon black, and fibres.
  10. A method for forming a stain resistant and soft tactile texture coating system onto a substrate, comprising the steps of:
    - forming a primer coating onto the substrate with a first composition comprising:
    a hydroxyl resin selected from one or more of the group consisting of alkyd resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, and modified silicone resins;
    a hardener resin having functional groups which react with hydroxyl groups of the hydroxyl resin;
    wherein the molar ratio of hydroxyl groups of the hydroxyl resin is excessive over the molar ratio of the functional groups of the hardener; and
    - forming a top coating onto the primer coating with a second composition comprising:
    an alkenyl containing polysiloxane of formula (I)
    Figure imgb0005
     wherein
    R represents an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
    R1 and R3 each independently represents an alkyl group having 1 to 8 carbon atoms;
    R2 represents an alkenyl group having 2 to 10 carbon atoms;
    l+m+n+a is within the range from 200 to 15000;
    wherein the alkenyl content of the alkenyl-containing polysiloxane is not less than 0.2 mmol/g and not greater than 5.0 mmol/g,
    a Si-H bond containing polysiloxane of the formula (II)
    Figure imgb0006
     wherein
    R4 and R5 each independently represents an alkyl group having 1 to 8 carbon atoms;
    R6 represents an alkyl group having 1 to 8 carbon atoms, or H;
    o+p+q+b is within the range from 5 to 500;
    a catalyst selected from one or more of the group consisting of platinum compounds, palladium compounds, rhodium compounds and ruthenium compounds.
  11. The article according to any one of claims 1-9, wherein the article is selected from the group comprising consumer electronic devices including mobile phones, tablets, personal computers, laptop computers, electronic readers, music players, computer accessories, televisions, game consoles, global positioning system devices, wearable devices; as well as automotive parts; home appliances, yachts, and aerospace crafts.
EP16925032.1A 2016-12-26 2016-12-26 A coating composition system, the preparation method, and the use thereof Active EP3559133B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/112126 WO2018119582A1 (en) 2016-12-26 2016-12-26 A coating composition system, the preparation method, and the use thereof

Publications (3)

Publication Number Publication Date
EP3559133A1 EP3559133A1 (en) 2019-10-30
EP3559133A4 EP3559133A4 (en) 2020-09-09
EP3559133B1 true EP3559133B1 (en) 2024-02-21

Family

ID=62706552

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16925032.1A Active EP3559133B1 (en) 2016-12-26 2016-12-26 A coating composition system, the preparation method, and the use thereof

Country Status (8)

Country Link
US (1) US11530333B2 (en)
EP (1) EP3559133B1 (en)
KR (1) KR102307181B1 (en)
CN (1) CN110114427B (en)
BR (1) BR112019011449B1 (en)
MX (1) MX2019007259A (en)
RU (1) RU2745513C2 (en)
WO (1) WO2018119582A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018119582A1 (en) 2016-12-26 2018-07-05 Akzo Nobel Coatings International B.V. A coating composition system, the preparation method, and the use thereof
RU190530U1 (en) * 2019-04-30 2019-07-03 Федеральное государственное бюджетное учреждение "4 Центральный научно-исследовательский институт" Министерства обороны Российской Федерации THE DEVICE OF AUTOMATED EVALUATION OF THE REALIZABILITY OF THE BATTLE TASK OF GROUPING ROCKET COMPLEXES
WO2020232568A1 (en) * 2019-05-17 2020-11-26 Dow Silicones Corporation Coating composition and its uses
US20230118447A1 (en) * 2020-01-27 2023-04-20 Momentive Performance Materials Inc. Hydrophobic coating compositions based on organic binders
CN113308190B (en) * 2021-06-11 2022-02-18 常熟理工学院 High-adhesion gradient layered fouling release type marine antifouling paint
KR102529937B1 (en) * 2021-11-01 2023-05-09 주식회사 제이에이치기업 Paint for preventing adhesion, graffiti, mold on the surface of buildings
CN116102958B (en) * 2021-11-09 2024-03-22 广东华润涂料有限公司 Solvent-based acid-curable coating compositions and articles coated therewith
CN114015352B (en) * 2021-11-16 2022-05-27 湖南创瑾技术研究院有限公司 High-transparency light pollution prevention coating and preparation method and application thereof
CN115637105B (en) * 2022-10-11 2023-09-05 江西省信合新材料科技有限公司 Matte heat-resistant wear-resistant electronic paint and preparation method and application thereof

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772066A (en) 1972-05-22 1973-11-13 Dow Corning Process of coating metal substrates with silicone elastomer
US4419407A (en) 1982-01-29 1983-12-06 Ppg Industries, Inc. Elastomeric coating compositions
JPS59152955A (en) * 1983-02-21 1984-08-31 Toshiba Silicone Co Ltd Curable silicone composition
JPS6279273A (en) * 1985-10-01 1987-04-11 Shin Etsu Chem Co Ltd Composition for coating material
US4877854A (en) * 1986-12-08 1989-10-31 Tokuyama Soda Kabushiki Kaisha Curable composition
IE76718B1 (en) 1987-08-03 1997-11-19 American Film Tech System and method for color image enhancement
JP2537981B2 (en) 1988-08-18 1996-09-25 カネボウ・エヌエスシー株式会社 Composition for elastic paint
JPH086069B2 (en) 1988-10-20 1996-01-24 東レ・ダウコーニング・シリコーン株式会社 Paint composition
US4971841A (en) * 1989-06-08 1990-11-20 Basf Corporation Reflective automotive coating compositions
DE4040306A1 (en) * 1990-12-17 1992-06-25 Behringwerke Ag METHOD FOR DETERMINING ANTIBODY AGAINST LIPOCORTINE
JP3508935B2 (en) 1991-05-30 2004-03-22 東レ・ダウコーニング・シリコーン株式会社 Paint composition
JP2787737B2 (en) 1991-06-28 1998-08-20 東レ・ダウコーニング・シリコーン 株式会社 Method for producing aqueous coating composition
DE4328657A1 (en) * 1993-08-26 1995-03-02 Bayer Ag Organopolysiloxane mixture for the production of adhesive-repellent organopolysiloxane films
FR2719598B1 (en) 1994-05-03 1996-07-26 Rhone Poulenc Chimie Silicone elastomer composition and its applications, in particular for the coating of an airbag, intended for the protection of a vehicle occupant.
JP3584410B2 (en) * 1994-09-01 2004-11-04 日本ペイント株式会社 Composite coating method
CA2179561A1 (en) 1995-06-27 1996-12-28 Hideki Takayama Coating composition and method for forming multi-layer coating
JPH10298488A (en) 1997-04-23 1998-11-10 Suzuka Fine Kk Elastic coating composition having excellent stain resistance and elastic coating composition for finishing
JPH11349897A (en) 1998-06-10 1999-12-21 Ge Toshiba Silicone Kk Coating material composition
KR100760068B1 (en) 1999-07-30 2007-09-18 피피지 인더스트리즈 오하이오, 인코포레이티드 Coating compositions having improved scratch resistance, coated substrates and methods related thereto
JP2001152095A (en) 1999-11-29 2001-06-05 Shin Etsu Chem Co Ltd Coating composition
US6432181B1 (en) * 2000-03-03 2002-08-13 Resource Development, L.L.C. Silicone compositions, methods of making and using VOC free, non-flammable creams, pastes and powders to render nonporous surfaces water, soil and stain repellent
US6592999B1 (en) 2001-07-31 2003-07-15 Ppg Industries Ohio, Inc. Multi-layer composites formed from compositions having improved adhesion, coating compositions, and methods related thereto
FR2840915B1 (en) 2002-06-18 2004-08-27 Ferrari S Tissage & Enduct Sa METHOD FOR COATING AN ARCHITECTURAL TEXTILE WITH AT LEAST ONE SILICONE ELASTOMER LAYER FROM AQUEOUS SILICONE EMULSION AND ARCHITECTURAL TEXTILE SO COATED
DE10227533C1 (en) * 2002-06-20 2003-12-11 Groz Beckert Kg Stitch transfer needle, for a knitter, has the mounting section of the stitch transfer spring securely bonded in place within a slit, which opens at one of the narrow sides of the needle body
US7396875B2 (en) 2003-06-20 2008-07-08 Bayer Materialscience Llc UV-curable waterborne polyurethane dispersions for soft touch coatings
JP4604539B2 (en) * 2004-04-06 2011-01-05 トヨタ自動車株式会社 Touch-sensitive body
EP1595902A1 (en) * 2004-05-10 2005-11-16 Sika Technology AG Polyurethane composition having high early strength
US20060024493A1 (en) 2004-07-28 2006-02-02 Jones R P Color effect/soft feel coating
US20060021888A1 (en) 2004-07-29 2006-02-02 Andre Kieran F Packaging for golf equipment using soft touch coating
US20060141264A1 (en) 2004-12-23 2006-06-29 Rearick Brian K Soft feel coating for a rigid substrate
KR100744399B1 (en) 2005-12-21 2007-07-30 삼성전자주식회사 Coating composition for soft feel coating composition using suface of electronic device and mobile phone and producing method thereof
US7407710B2 (en) 2006-04-14 2008-08-05 3M Innovative Properties Company Composition containing fluoroalkyl silicone and hydrosilicone
TW200813159A (en) 2006-04-26 2008-03-16 Dow Corning Korea Ltd A liquid silicone rubber composition for forming breathable coating film on a textile and process for forming a breathable coating film on a textile
KR100828789B1 (en) 2006-07-05 2008-05-09 현대자동차주식회사 Thinwall Waterborne Soft Feel Paint
AU2007283772B2 (en) * 2006-08-04 2013-03-07 Kensey Nash Corporation Biomimetic compounds and synthetic methods therefor
CA2679687A1 (en) 2007-03-02 2008-09-12 Akzo Nobel Coatings International B.V. Water borne soft-feel coating composition
AU2008244255B2 (en) * 2007-05-01 2013-08-29 Akzo Nobel Coatings International B.V. Antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymers
JP2009007468A (en) 2007-06-28 2009-01-15 Shin Etsu Chem Co Ltd Liquid silicone rubber coating composition for curtain air bag, curtain air bag, and manufacturing method therefor
US8772407B2 (en) * 2007-09-17 2014-07-08 Ppg Industries Ohio, Inc. One component polysiloxane coating compositions and related coated substrates
CN101168621A (en) 2007-11-23 2008-04-30 东莞市贝特利新材料有限公司 Organic silicon hand feeling protection oil and preparation method thereof
CN101619181B (en) 2009-07-31 2011-04-06 广东嘉宝莉化工集团有限公司 Soft hand feel coating and preparation method thereof
JP5397350B2 (en) 2009-09-11 2014-01-22 信越化学工業株式会社 Liquid silicone rubber coating composition, curtain airbag and method for producing the same
MX2012003993A (en) 2009-10-26 2012-08-15 Dow Corning Organosiloxane compositions.
CN102002166B (en) 2010-10-11 2012-07-04 中国海洋石油总公司 Hydroxylated polyurethane water dispersoid for waterborne soft-feel coating and preparation method thereof
WO2012089827A1 (en) 2010-12-30 2012-07-05 BECKERS HIGH PERFORMANCE COATINGS (TIANJIN) Ltd. Soft touch coating composition
KR101244640B1 (en) 2011-01-20 2013-03-18 주식회사 케이씨씨 Liquid silicone rubber coating composition and airbag with cured film thereof
CN102898945B (en) 2011-07-28 2016-03-02 比亚迪股份有限公司 Silica gel feel oil and preparation method thereof and silica gel product and preparation method thereof
US9567488B2 (en) * 2012-07-03 2017-02-14 Burning Bush Group, Llc High performance silicon based coating compositions
JP6072066B2 (en) * 2012-11-13 2017-02-01 中国塗料株式会社 Curable organopolysiloxane antifouling composite coating and antifouling substrate coated with the composite coating
US20160194455A1 (en) * 2013-09-25 2016-07-07 Alzo International, Inc Silicone Elastomer Gels and Related Hydrosilylation Processes
GB201402179D0 (en) 2014-02-07 2014-03-26 Dow Corning Surface treatment
JP6594991B2 (en) * 2015-03-05 2019-10-23 ダウ・東レ株式会社 Curable organopolysiloxane composition, use of the composition, and laminate made from the composition
WO2018119582A1 (en) 2016-12-26 2018-07-05 Akzo Nobel Coatings International B.V. A coating composition system, the preparation method, and the use thereof

Also Published As

Publication number Publication date
KR20190086751A (en) 2019-07-23
BR112019011449A2 (en) 2019-10-08
CN110114427B (en) 2022-03-18
RU2019122599A3 (en) 2021-01-26
MX2019007259A (en) 2019-09-05
BR112019011449B1 (en) 2022-11-01
US11530333B2 (en) 2022-12-20
RU2745513C2 (en) 2021-03-25
EP3559133A4 (en) 2020-09-09
RU2019122599A (en) 2021-01-26
KR102307181B1 (en) 2021-09-30
US20190330494A1 (en) 2019-10-31
WO2018119582A1 (en) 2018-07-05
EP3559133A1 (en) 2019-10-30
CN110114427A (en) 2019-08-09

Similar Documents

Publication Publication Date Title
EP3559133B1 (en) A coating composition system, the preparation method, and the use thereof
TWI622625B (en) Organosiloxane compositions and coatings, manufactured articles, methods and uses
Chen et al. Effects of surface properties of colloidal silica particles on redispersibility and properties of acrylic-based polyurethane/silica composites
CA2523691C (en) Mold release composition and process therewith
JP5737840B2 (en) Composition having an anti-mist component
CN101400736B (en) Anti-fouling polyaddition silicone varnish, application of said varnish to a support and support treated thus
WO2019182860A1 (en) Silicone polymer and composition comprising the same
TW201930477A (en) Additive organopolysiloxane composition, curable composition, and film
JP2021520421A (en) Self-adhesive silicone elastomer
CN114641541B (en) Additive for water-based paint, water-based paint composition and coating
JP2016113610A (en) Soft feel coating composition for one time coating
JP2831877B2 (en) Emulsion composition
TWI662060B (en) Silicone-containing polyesters, coating compositions containing the same, and coatings formed therefrom
JP3183109B2 (en) Organopolysiloxane composition, surface treating agent and silicone rubber part
TWI808232B (en) Coating composition comprising polysiloxane-modified polyurethane for soft-feel, stain resistant coatings
JP3248322B2 (en) Film-forming silicone resin composition and molded silicone resin
RU2522614C2 (en) Method of improving adhesion to metals of silicon composite materials, obtained by reaction of polyaddition
JP2013129758A (en) Excellently scratch-resistant one-part clear coating composition for autompbile obtained by applying silane-modified blocked isocyanate
PL235480B1 (en) Process for preparing a two-component varnish or paint resin of glycidylsiloxane cured by triethylenetetramine at the elevated temperature
JP2000007998A (en) Luster agent

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190524

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20200807

RIC1 Information provided on ipc code assigned before grant

Ipc: C08J 7/04 20200101ALI20200803BHEP

Ipc: C09D 167/02 20060101ALI20200803BHEP

Ipc: C09D 183/07 20060101ALI20200803BHEP

Ipc: C09D 183/05 20060101AFI20200803BHEP

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AKZO NOBEL COATINGS INTERNATIONAL B.V.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C09D 167/02 20060101ALI20230920BHEP

Ipc: C08J 7/04 20060101ALI20230920BHEP

Ipc: C09D 183/07 20060101ALI20230920BHEP

Ipc: C09D 183/05 20060101AFI20230920BHEP

INTG Intention to grant announced

Effective date: 20231005

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016085961

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

U01 Request for unitary effect filed

Effective date: 20240223

U07 Unitary effect registered

Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI

Effective date: 20240301